Sulphonium naphthalimides

ABSTRACT

THIS INVENTION RELATES TO NEW SALTS OF SULPHONIUM DERIVATIVES OF NAPHTHALIMIDE. THESE SALTS HAVE THE GENERAL FORMULA:   1,3-DI(O=),2-(R2-S(+)(-R1)-(CH2)N-),7-(R-O-)-2,3-DIHYDRO-   1H-BENZ(DE)ISOQUINOLINE   IN WHICH R AND R1 EACH REPRESENT THE SAME OR DIFFERENT LOWER ALKYL RADICALS, PREFERABLY METHYL OR ETHYL, R2 REPRESENTS A LOWER ALKYL RADICAL WHICH MAY BE SUBSTITUTED BY A NON-IONIC AND NON-CHROMOPHORIC SUBSTITUENT SUCH AS FOR EXAMPLE A LOWER ALKOXYGROUP, N REPRESENTS A WHOLE NUMBER GREATER THAN 1, PREFERABLY 2 OR 3, AND AO REPRESENTS A MONOVALENT ANION.

United States Patent O 3,642,799 SULPHONIUM NAPHTHALIMIDES GeorgesRaymond Henry Mingasson, Paris, Annick Marthe Suzanne Simone Domergue,Eanbonne, and Robert Frederic Michel Sureau, Enghien les Baines, France,assignors to Ugine Kulllmann, Paris, France No Drawing. Filed July 29,1969, Ser. No. 846,999 Claims priority, application France, Aug. 16,1968, 161,965 Int. Cl. C07d 35/30 US. Cl. 260-270 R Claims ABSTRACT OFTHE DISCLOSURE This invention relates to new salts of sulphoniumderivatives of naphthalimide. These salts have the general formula:

- N( CH2) n% The present invention relates to new salts of sulphoniumderivatives of naphthalimide and corresponding to the general formula:

in which R and R each represent the same or different lower alkylradicals, preferably methyl or ethyl, R represents a lower alkyl radicalwhich may be substituted by a non-ionic and non-chromophoric substituentsuch as for example a lower alkoxy group, n represents a whole numbergreater than 1, preferably 2 or 3, and A represents a monovalent anion.

Lower alkyl radicals and lower alkoxy radicals referred to throughoutthe specification are those containing from 1 to 4 carbon atoms.

The compounds of Formula I are very soluble in water, and their aqueoussolutions show in daylight an intense greenish blue fluorescence. Theircationic character gives them, besides water-solubility, an excellentaffinity for fibres based on polymers or copolymers of 'acrylonitrile,to which they impart a whitening effect of a particularly valuablebrilliance, which is stable to light and to aftersetting and resistantto washing and chemical bleaching agents such as sodium chlorite.

The optical brightening agents of Formula I may be prepared for exampleby the action of an alkylating agent of Formula AR for example an alkylhalide, sulphate, or sulphonate, on a compound of the general formula:

in which A, R, R R and n have the same significance as in Formula I.This reaction may be carried out without a solvent or in the presence ofan organic solvent such as for example aromatic hydrocarbons or theirchlorinated derivatives, alcohols, chloroform or dimethyl formamide. Thecompounds of Formula II are new products. They may be prepared forexample by condensing 4-bromo naphthalic anhydride with an amine of theformula:

in an aqueous medium or an organic solvent such as an alcohol orhydrocarbon, at a temperature from C. to 200 C. and treating the newbromonaphthalimide thus obtained of formula:

with an alkali metal alcoholate in an excess of an anhydrous alcoholicmedium at the boil or under pressure. In formulae (III) and (IV), thesymbols R and n have the same significance as in Formula I.

The compounds of Formula II may also be obtained for example bycondensing a 4-alkoxy-naphthalic anhydride With an amine of Formula IIIThe invention is illustrated by, but not limited to, the followingexamples in which the parts are by weight unless the contrary isindicated. Examples 1 to 10 illustrate the preparation of theintermediate products of Formulae II and IV. Examples 11 to 15, 17 and18 illustrate the preparation of sulphonium derivatives ofnaphthalimides according to the invention.

NAPHTHALIMIDES OF FORMULA IV Example 1 A mixture of 56 parts of4-bromo-naphthalic anhydride, 18.2 parts of fl-aminoethylmethyl sulphideand 400 parts of ethyl alcohol is heated under reflux, with stirring,for

5 hours. Solution first takes place, then the bromonaphthalimide isreprecipitated. After cooling, the precipitate is filtered off, washedwith ethyl alcohol and dried. 64 parts of4-bromo-N-(2-methyl-thio-ethyl)-naphthalimide melting at 128 C. areobtained.

On replacing the ethyl alcohol with the same amount of Water, anidentical product is obtained.

Example 2 The procedure is as in Example 1, but the ,B-aminoethylmethylsulphide is replaced by 21 parts of 'y-aminopropylmethyl sulphide. 30parts of 4-bromo-N-(3-methylthiopropyl)-naphthalimide melting at C. areobtained.

Example 3 A" mixture of 8.4 parts of 4-bromo-naphthalic anhydride, 5parts of ,B-aminoethyl-fl-ethoxyethylsulphide and 65 parts of ethanol isheated under reflux for 5 hours, with stirring. The product formed isfiltered off after cooling and dissolved in 30 parts of boiling benzene.The solution is decolorised by the addition of carbon black andfiltered. On addition of 30 parts of petrol ether, 9.3 parts of a whitecrystalline precipitate melting at C. consisting of 4bromo-N-[2-(2"-eth0xy-ethylthio) ethyl]- naphthalimide are formed.

When recrystallised from ethanol, this compound melts at 12l122 C. andits analysis gives the following results:

Calculated for C H B1NO S (percent): C, 52.90; H, 4.42; N, 3.43; S,7.84. Found (percent): C, 53.1; H, 4.94; N, 3.6; S, 7.76.

The B-aminoethyl l3-ethoxyethyl sulphide used in this example wasobtained in the following way; 10.6 parts of [i-ethoxyethane-thiol areintroduced into a cold solution of 8.8 parts of caustic soda in 60 partsby volume of absolute ethanol. 11.6 parts of fl-chloroethylaminehydrochloride are added and the mixture is heated at 5060 C. for 2hours, then under reflux for 3 hours. The product is cooled to C.,filtered and the solid washed with alcohol. The alcoholic solution isevaporated and the residue is extracted with 40 parts by volume ofbenzene. The benzene is distilled and the mixture is rectified undervacuum. 11.2 parts of B-aminoethyl-B-ethoxyethyl sulphide are thusobtained. B.P. 18=115 C. Titre=96%.

NAPHTHALIMIDES OF FORMULA II Example 4 7 parts of the bromonaphthalimidedescribed in Example 1 are heated with 80 parts of methanol containing 2parts of sodium at 105 C. for 3 hours in a sealed tube. After cooling,the crystalline product is filtered off, washed with a little methanol,then with water until neutral. After drying, parts of4methoxy-N-(2-methylthioethyl)- naphthalimide are obtained in the formof a clear yellow product melting at 127 C.

After recrystallising from ethanol, analysis gives the followingresults:

Calculated for C H NO S (percent) C, 63.7; H, 4.98; N, 4.65; S, 10.63.Found (percent): C, 63.13; H, 5.01; N, 4.60; S, 10.71.

Example 5 On operating as in Example 4 from 7.2 parts of thebromonaphthalimide described in Example 2, 80 parts of methanol and 2parts of sodium, 5.1 parts of 4-methoxy-N-(3'-methylthio-propyl)-naphthalimide melting at 93 C. are obtained.

After recrystallising from ethanol, analysis gives the followingresults:

Calculated for C H NO S (percent): C, 64.7; H, 5.39; N, 4.4; S, 10.1.Found (percent): C, 64.05; H, 5.7; N, 4.51; S, 10.12.

Example 6 On operating as in Example 4 from 7 parts of thebromonaphthalimide described in Example 3, 125 parts of absolutemethanol and 2 parts of sodium, an oily product is obtained whichcrystallises on cooling. After filtering, washing with water untilneutral and drying in vacuo, 5.6 parts of4-methoxy-N-[2'-(2-ethoxy-ethylthio)-ethyl]- naphthalimide melting at 70C. are obtained.

After recrystallising from methanol, the product melts at 76 C. and itsanalysis gives the following results:

Calculated for C H O NS (percent): C, 63.50; H, 5.85; N, 3.90; S, 8.92.Found (percent): C, 63.8; H, 6.53; N, 3.50; S, 8.60.

Example 7 A mixture of 2.3 parts of 4-methoxy-naphthalic anhydride, 1part of /3-amin0ethylmethy1 sulphide and parts of ethylene glycol areheated with stirring at 115 C. for 5 hours. The product is left to cool,the precipitate is filtered off, washed with alcohol then with water anddried. The product obtained melts at 127 C. It is identical with that ofExample 4.

Example 8 On replacing the fi-aminoethylmethyl sulphide in Example 7 by1.1 parts of 'y-aminopropylmethyl sulphide, the methoxynaphthalimidedescribed in Example 5 is obtained.

Example 9 On replacing the methanol in Example 4 by an equal quantity ofabsolute ethanol, 5 parts of 4-ethoxy-N-(2-methylthio-ethyl)-naphthalimide are obtained which, afterrecrystallising from ethanol, melts at 133 C.

Example 10 On proceeding as in Example 5, but replacing the methanol byethanol, 4.4 parts of 4-ethoxy-N-(3'-methylthiopropyl)-naphtha1imide areobtained which, after recrystallising from ethanol, melts at 122 C.

NAPHTHALIMIDES OF FORMULA I Example 11 CO J This product is soluble inWater with an intense blue fluoroescence.

ea/C II; N-CH3 O II S Example 12 On replacing in the preceding examplethe 4-methoxy- N (2' methylthio-ethyl)-naphthalimide by 4-meth0xy- N (3'methylthio-propyl)-naphthalimide, 4'-methoxy- 3naphthalimido-propyldimethyl sulphonium chlorozincate is obtained in thesame way.

Examples 13 and 14 On operating as in Example 11 from the 4-ethoxy-N-(2'-methylthio-ethyl)-naphthalimide described in Example 9 or from the4-ethoxy-N-(3'-methylthio-propyl)- naphthalimide described in Example10, 4 ethoxy-2- naphthalimido-ethyl dimethylsulphonium chlorozincate and4' ethoxy 3 naphthalimido-propyl-dimethyl sulphonium chlorozincate areobtained respectively.

Example 15 A mixture of 2 parts of4-methoxy-N-[2'-(2"-ethoxyethylthio)-ethyl]-naphthalimide described inExample 6 and 2 parts of methyl sulphate is heated at C. for one hour.At the end of about 45 minutes, the initial solution solidifies to acrystalline pulp. The' mass is diluted with 10 parts of water, thesolution obtained is boiled with 0.2 part of carbon black and filtered.2 parts of sodium chloride are added to the cooled solution, then 10parts by volume of a 10% solution of zinc chloride are added graduallywith stirring. After filtering and drying, 3.2 parts of a pale yellowcrystalline product are obtained. When recrystallised from anhydrousethyl alcohol, its analysis gives the following results:

Calculated for C H ClNO S, /2 ZnCl (percent): C, 50.25; H, 5.02; S,6.70; N, 2.93. Found (percent): C, 49.7; H, 5.47; S, 7.17; N, 3.06.

Example 16 A treatment bath is prepared by dissolving 0.4 parts of oneof the sulphonium salts described in Examples 11 to 15 in 3000 parts ofwater and 4 parts of acetic acid. parts by volume of a 5% solution ofsodium chlorite are added and 100 parts of a fabric based onpolyacrylonitrile are introduced. The bath is heated to boiling in Amixture of 3 parts of 4-methoxy-N-(2'-methylthioethyl)-naphthalimide and3 parts of ethyl sulphate is heated at 70-80" C. for one hour on a waterbath. After cooling, the mass is diluted with 40 parts of water, alittle carbon black is added, and it is brought to reflux and filtered.Sodium chloride is added to the cooled solution, then a dilute solutionof zinc chloride. After filtering and drying, 4methoxy-Z-naphthalimido-ethyl-ethyl-rnethylsulphonium chlorozincate isobtained.

On replacing the addition of sodium chloride and zinc chloride by anaddition of potassium iodide, 4'-methoxy- 2naphthalimido-ethyl-ethyl-methylsulphonium iodide is obtained.

Example 18 A mixture of 3 parts of4-methoxy-N-(2-methylthioethyl)-naphthalimide and 3 parts of methylp-toluenesulphonate is heated at 100 C. for 30 minutes. The solidproduct obtained on cooling is washed with a little chloroform anddried. 1.6 parts of 4-methoxy-2-naphthalimidoethyl-dimethylsulphoniump-toluene-sulphonate in the form of a clear yellow powder which iscompletely soluble in water are thus obtained.

The sulphonium salts described in Examples 17 and 18 may be applied tofibres based on polymers or copolymers of acrylonitrile by the processdescribed in Examples 16 with analogous results.

We claim:

1. A water-soluble optical brightening agent of the formula:

in which R and R each are the same or different lower alkyl groups, R isa lower alkyl or lower alkoxyalkyl group, n is 2 or 3 and A is acolourless monovalent anion.

8. The 3 (4' methoxy-naphthalimido)propyl dimethyl sulphoniumsulphomethylate.

9. The 2 (4 ethoxy-naphthalimido)ethyl dimethyl sulphoniumchlorozincate.

10. A process for the preparation of an optical brightening agent inwhich a compound of the formula:

in which R is a lower alkyl group, n is 2 or 3, and R is a lower alkylor lower alkoxyalkyl group is reacted with a lower alkyl halide,sulphate or sulphonate.

References Cited UNITED STATES PATENTS 3,308,127 3/1967 Senshu 260-2813,310,564 3/1967 Kasai 260-281 3,330,834 7/1967 Senshu et a1. 260-281DONALD G. DAUS, Primary Examiner U.S. Cl. X.R.

UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No. 3, ,799Dated February 15, 1972 Inventor(s) G.R.H. Mingasson, A M,S,S, Domer'gueand R,F. M, Sureau It is certified that error appears in theabove-identified patent and vthat said Letters Patent are herebycorrected as shown below:

In the heading, column 1, lines 5 and 6 should read:

Claims priority, application France, Aug. 6, 1968,

' Signed and sealed this 13th day of June 1972.

(SEAL) Attest:

EDWARD M.FLETCHER,JR. ROBERT GOTTSCHALK Attesting Officer Commissionerof Patents FORM PO-10SO (10-69) USCOMM-DC 60376-1 69 u.s. GOVERNMENTPRINTING OFFICE: I969 0-366-334

